CN103249702A - The use of Anderson -type heteropoly compound - based catalyst compositions in the conversion of synthesis gas to oxygenates - Google Patents
The use of Anderson -type heteropoly compound - based catalyst compositions in the conversion of synthesis gas to oxygenates Download PDFInfo
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- CN103249702A CN103249702A CN2011800590037A CN201180059003A CN103249702A CN 103249702 A CN103249702 A CN 103249702A CN 2011800590037 A CN2011800590037 A CN 2011800590037A CN 201180059003 A CN201180059003 A CN 201180059003A CN 103249702 A CN103249702 A CN 103249702A
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- catalyzer
- cobalt
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- water
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims description 32
- 230000015572 biosynthetic process Effects 0.000 title abstract description 4
- 238000003786 synthesis reaction Methods 0.000 title abstract description 3
- 238000006243 chemical reaction Methods 0.000 title description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 26
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 26
- 239000010948 rhodium Substances 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 229910017052 cobalt Inorganic materials 0.000 claims description 17
- 239000010941 cobalt Substances 0.000 claims description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052703 rhodium Inorganic materials 0.000 claims description 17
- 229910052763 palladium Inorganic materials 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 229910052741 iridium Inorganic materials 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- -1 magnesium aluminate Chemical class 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 7
- 229960001866 silicon dioxide Drugs 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 229910052728 basic metal Inorganic materials 0.000 claims description 5
- 150000003818 basic metals Chemical class 0.000 claims description 5
- 229910052702 rhenium Inorganic materials 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 56
- 239000000243 solution Substances 0.000 description 50
- 239000007864 aqueous solution Substances 0.000 description 46
- 229910019837 RhMo Inorganic materials 0.000 description 36
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 17
- 229910020068 MgAl Inorganic materials 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 229910004298 SiO 2 Inorganic materials 0.000 description 12
- 229910052750 molybdenum Inorganic materials 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 238000001354 calcination Methods 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 7
- 235000018660 ammonium molybdate Nutrition 0.000 description 7
- 239000011609 ammonium molybdate Substances 0.000 description 7
- 229940010552 ammonium molybdate Drugs 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 239000002178 crystalline material Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 3
- 229910052762 osmium Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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- 241000220317 Rosa Species 0.000 description 2
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
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- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 210000000056 organ Anatomy 0.000 description 2
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- 239000011591 potassium Substances 0.000 description 2
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- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- FPFSGDXIBUDDKZ-UHFFFAOYSA-N 3-decyl-2-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCCCCCC1=C(O)C(=O)CC1 FPFSGDXIBUDDKZ-UHFFFAOYSA-N 0.000 description 1
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- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
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- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
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- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
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- 238000006703 hydration reaction Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- FMEVCTOFYHBTTB-UHFFFAOYSA-N iridium molybdenum Chemical compound [Mo].[Ir].[Ir].[Ir] FMEVCTOFYHBTTB-UHFFFAOYSA-N 0.000 description 1
- KWUUWVQMAVOYKS-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe][Mo][Mo] KWUUWVQMAVOYKS-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 230000007115 recruitment Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- FZFRVZDLZISPFJ-UHFFFAOYSA-N tungsten(6+) Chemical compound [W+6] FZFRVZDLZISPFJ-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
- C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
- C07C29/158—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof containing rhodium or compounds thereof
-
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
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- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
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- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
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- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
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Abstract
Use a transition metal-containing, Anderson-type heteropoly compound catalyst to convert synthesis gas to an oxygenate, especially an alcohol that contains from one carbon atom to six carbon atoms.
Description
The application is non-provisional application, require the U.S. Provisional Patent Application 61/391 that is entitled as " ANDERSON-TYPE HETEROPOLY-BASED CATALYST COMPOSITIONS AND THEIR USE CONVERSION OF SYNTHESIS GAS TO OXYGENATES " of submission on October 11st, 2010,735 right of priority, incorporate the instruction of the document into the application by reference, just as it is reproduced among the application in full.
The present invention generally relates to catalyst composition, and it is used for synthetic gas (synthetic gas, carbon monoxide (CO) and hydrogen (H based on Anderson type structure heteropoly compound and they
2) mixture) change into the purposes of oxide compound, described oxide compound especially contains 2 to 6 carbon atom (C
2To C
6) alcohol.
The synthetic gas method for transformation uses various catalyzer, often produces mixture of products (for example hydrocarbon such as ethane and propane, the hydrocarbon of oxidation is methyl alcohol for example, ethanol, propyl alcohol and butanols) thus.Those people that put into practice this method continue to seek method and the catalyzer of improvement, it provides the product mixtures that tends to the selective oxidation thing for hydrocarbon more, and at least some practitioners wherein are with respect to other oxide compounds for example for the methyl alcohol, more be partial to some oxide compound, for example propyl alcohol.With respect to the challenge that methanol conversion is become alkene, this deflection is at least part of to be come from easily with C
2To C
6Oxygenate conversion becomes corresponding alkene.
Anderson type heteropoly compound can be by general formula [A]
N+[XM
6O
24H
x]
N-(wherein X is the heteroatoms Al for example that is positioned at the center, or transition metal Co for example, and Ni, Rh, A are for example H of positively charged ion in expression
+, (NH
4 +), alkalimetal ion is selected from the metal ion of transition metal ion, and M is at least a among Mo and the W), n
-Be the net negative charge of anionicsite, n
+It is cationic clean positive charge.Anderson-type heteropoly compound is categorized as A type (x=0) and Type B (x=6) according to attached proton number, but has reported that also x is not some polyanionics of 0 or 6.
People such as K.Nomiya are at " Anderson-Type Heteropolyanions of Molybdenum (VI) and Tungsten (VI) ",
Polyhedron, Volume6, Number2, pages213-218 (1987), middle part has disclosed the polyanionic research of B-type molybdenum, especially contains those of divalent-metal ion (Zn (II), Cu (II), Co (II) or Mn (II)) except Ni (II).They have also studied Ni (II) polyanionic that mixes, and wherein the M in the following formula is the mixture of molybdenum (Mo) and tungsten (W).
People such as C.Cabello are at " Anderson Type heteropolyoxomolybdates in catalysis:1. (NH
4)
3[CoMo
6O
24H
6] 7H
2O/ γ-Al
2O
3As alternative of Co-Mo/ γ-Al
2O
3Hydrotreating catalysts ",
Applied Catalysis A:General197, pages79-86 (2000), in provided about preparation Co-Mo/ γ-Al
2O
3The instruction of the method for HDS (hydrogenating desulfurization effect) catalyzer is used in the method and is supported on γ-Al
2O
3On (NH
4)
3[CoMo
6O
24H
6] 7H
2The O Anderson type polyoxy molybdate of mixing.
People such as C.I.Cabello are at " Catalysts based on RhMo
6Heteropolymetallates.Bulk and supported preparation and characterization ",
Studies in Surface Science And Catalysis, 143, Elsevier Science B.V. (2002), pages565-572 has mentioned existing research to a series of six metallides (hexametallate), this six metallide is called Anderson[XM
6O
24H
6]
3-, wherein M=Mo, W or Mo
(6-x)W
xAnd X=Co (III), Rh (III), Fe (III), Mi (II), Cu (II), Fe (VI), etc., this makes it possible to design and make two-or the three-metallographic phase of various mixing, this metallographic phase demonstrates structure and redox property, and may be used for the heterogeneous catalysis application as hydrogen treatment and oxidative ammonolysis.
People such as I.L.Botto are at " (NH
4)
6[TeMo
6O
24] 7H
2O Anderson phase as precursor of the TeMo
5O
16Catalytic phase:thermal and spectroscopic Studies ",
Materials Chemistry and Physics47 (1997) pages37-45, the middle formula [XMo that characterized
6O
24H
6]
N-Anderson type heteropolyanion, wherein X is for example Te, Fe, Co, Al, Ga, Rh, Ni, or Zn.
People such as T.Liu are at " Structures and Catalytic Activity of Pt-Mo Bimetallic Ensembles Derived from a New Planar[PtMo
6O
24]
8-Heteropolyanion Supported on Al
2O
3And SiO
2",
Journal of Catalysis135 (1992), pages367-385, in provided instruction about title substance in ethene hydrogenation and the ethane hydrogenolysis.
People such as C.Lamonier are at " Molybdocobaltate cobalt salts:New starting materials for hydrotreating catalysts ",
Applied Catalysis B:EnvironmentalHandled among 70, the pages548-556 (2007) and used the Anderson heteropolyanion to contain oxygen precursor (oxidic precursors) as the optional initial substance of Ammonium Heptamolybdate and Xiao Suangu for the preparation of hydrogen treatment (for example hydrogenating desulfurization effect of thiophene).They have instructed preparation Anderson molybdenum cobaltates ((NH
4)
3[CoMo
6O
24H
6]) or molybdenum aluminate ((NH
4)
3[AlMo
6O
24H
6]) ammonium salt.
English Patent (GB) 2151616 (Jackson) has disclosed by making synthetic gas at the hydrocarbon of the temperature that raises and the oxidation of catalyzer contact preparation (methyl alcohol for example, ethanol and propyl alcohol) method, described catalyzer comprises group VIII (periodic table of elements) metal component (iron (Fe), the cobalt (Co) that is supported on Tungsten oxide 99.999 or the molybdenum oxide, nickel (Ni), Ru, Rh, palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt), especially rhodium (Rh)).
US4,749,724 (people such as Quarderer) have disclosed the Fischer-Tropsch reaction, and its use contains at least a Mo, the W of form free or combination and the element of Re of being selected from, the catalyzer of basic metal or alkaline-earth metal promotor and optional carrier forms alcohol from synthetic gas.This catalyzer can contain for example zinc (Zn) of limited amount component, copper (Cu) and Co.
In some respects, the present invention is the method that synthetic gas is changed into oxide compound, this method comprises that the mixture that makes hydrogen and carbon monoxide contacts under the condition of the temperature that is enough to this mixture is changed at least a alcohol, pressure and gas hourly space velocity with the Anderson type Heterocompound catalyst that contains transition metal, wherein said alcohol contains 1 to 6 carbon atom, and described catalyzer has by general formula (A)
x[M
1Mo
yW
6-y] M
2The structure of expression, wherein A is H
+, ammonium ion ([NH
4])
+, or alkalimetal ion, M
1Be aluminium, zinc or chosen from Fe, ruthenium, chromium, rhodium, copper, cobalt, nickel, at least a in the transition metal of palladium and iridium, M
2Be the properties-correcting agent metal of choosing wantonly, it is to be selected from following at least a metal: basic metal, and alkaline-earth metal and be selected from rhenium, chromium, palladium, cobalt, iridium, nickel, platinum, the transition metal of ruthenium and osmium, x are 3 to 4 integers, y is 0 to 6 integer.
Described temperature, pressure and gas hourly space velocity condition comprise following at least a: 200 degrees centigrade (° C) to the temperature of 450 ° of C scopes, 200psig (1.38MPa) is to pressure or the 300hr of 4,000psig (24.58MPa)
-1To 25,000hr
-1Gas hourly space velocity.
Gaseous hydrogen (the H that the mixture of hydrogen and carbon monoxide has
2) with the ratio of carbon monoxide (CO) be 10:1 to 1:10.
Above catalyzer comprises Anderson type heteropoly compound part and optional carrier part.When catalyzer comprises carrier part, the amount that this carrier exists for greater than 0 weight percent (wt%) to being not more than 95wt%, be preferably greater than or equal 40wt% to being not more than (being less than or equal to) 90wt%, in each case all based on the gross weight of catalyzer.When this catalyzer comprises carrier, Anderson type heteropoly compound part, i.e. (A)
x[M
1Mo
yW
6-y] M
2(abbreviate " [M sometimes in this application as
1Mo
yW
6-y] M
2"), exist with the amount of replenishing, for 5wt% at least at most but do not comprise 100wt%, equally based on the gross weight of catalyzer.Described magnitude of recruitment is preferably more than or equals 10wt% to being not more than (being less than or equal to) 60wt%, same gross weight based on catalyzer.
In this heteropoly compound part, the amount that A exists is 0.6wt% to 40wt%, is preferably 2wt% to 25wt%, M
1The amount that exists is 1.4wt% to 16wt%, is preferably 4wt% to 10wt%, and the amount that Mo exists is 0wt% to 58wt%, is preferably 12wt% to 50wt%, and the amount that W exists is 0wt% to 73wt%, is preferably 14wt% to 45wt%, optional component M
2The amount that exists is 0wt% to 20wt%, is preferably 2wt% to 10wt%, and each wt% is based on the gross weight of heteropoly compound.
M
1Be to be selected from Rh, Co, Ni, Pd, Zn, Al, Ru, Fe, Pt, Mn, one or more metals of Cr and Ir.M
1Be preferably Rh, Co or Ni.In some respects, M
1Be the combination of cobalt and palladium, the combination of cobalt and rhodium, the combination of aluminium and rhodium, the combination of cobalt and aluminium, the combination of copper and cobalt, and the combination of zinc and cobalt, y is 6.
This catalyzer can comprise that also the Anderson more than a type mixes polyoxy for compound.Therefore, in some respects, this catalyzer comprises the mixture of at least two kinds of Anderson type Heterocompound catalysts, M in first kind
1Be rhodium, M in second kind
1Be selected from cobalt, iridium, copper, nickel, palladium, zinc, aluminium, iron, chromium, and ruthenium.
M
2, when existing, be the properties-correcting agent metal, it is to be selected from basic metal, at least a metal in alkaline-earth metal and the transition metal, described transition metal are selected from rhenium (Re), Cr, Pd, Co, Ir, Ni, Pt, Ru, and Os.Basic metal comprises sodium, potassium, and lithium, rubidium, francium and caesium, sodium wherein, potassium and lithium are preferred.Alkaline-earth metal comprises calcium, barium, and strontium and radium, wherein calcium or barium are preferred.M
2Transition metal option preferably Re, Cr, Pd, Co, Ir and Ni.M
2, when existing, can but must not be and select to be used for M
1Same metal.
Carrier part is preferably selected from silicon-dioxide (SiO
2), zirconium white (ZrO
2), aluminum oxide (Al
2O
3), titanium oxide (TiO
2), Tungsten oxide 99.999 (WO
3), magnesium oxide (MgO), zinc oxide (ZnO), ZrO
2And Al
2O
3Mixture, be also referred to as the aluminum oxide of zirconium white-modification, be expressed as ZrO in each case
2-Al
2O
3, magnesium aluminate (MgAl
2O
4), Zinc aluminate (ZnAl
2O
4) and the carrier of MgO modification MgO-Al for example
2O
3And MgO-SiO
2
Anderson type heteropoly compound can prepare according to the method that people such as K.Nomiya (cited above) describe.These methods relate to preparation A type and Type B Anderson type heteropoly compound, and wherein M=Mo or W, X are divalence or trivalent metal ion for example Zn (II) or Al (III).This method always comprises and is prepared as follows molybdenum polyanionic or tungsten polyanionic: add the aqueous solution of metal sulfate or aluminum oxide in the boiled water solution of hydration Ammonium Heptamolybdate, further evaporate in steam bath, then filter this hot solution and cooling.
Arabic numerals are represented embodiments of the invention (Ex), and capitalization is represented Comparative Examples (Comp Ex or CEx).
Ex1
Under agitation with room temperature (being generally 25 ° of C), dropwise add 0.5 gram (g) 30% hydrogen peroxide (H
2O
2) aqueous solution is to the aqueous solution (CoSO of rose vitriol
4.4H
2O, S.D.Fine, 1.04g are dissolved in the water of 8 milliliters (mL)) in, thereby form first solution.Under 90 minutes situation of 95 ° of C stirrings, this first solution is added into second the solution ((NH of 7.65g Ammonium Heptamolybdate
4)
6Mo
7O
244H
2O, Acros Chemicals) be dissolved in the 65mL water) middle the 3rd solution that forms.Stop to stir and allowing that the 3rd solution left standstill spends the night.By filtering and 80 ° of C dryings, reclaiming the green crystal powder from the 3rd solution, be expressed as (NH
4)
3[CoMo
6O
24H
6] .7H
2O, the assorted polyoxy of a kind of Anderson type is abbreviated as [CoMo in this application for molybdate
6].
Ex2
Repeat Ex1, difference is that the aqueous solution (Fluka, 0.45g are dissolved in the 20mL water) with rhodium nitrate replaces this first solution, and this second solution is joined 2.60g is dissolved in (NH in the 40mL water
4)
6Mo
7O
244H
2O.Reclaim the yellow crystal powder from the 3rd solution.This powder is expressed as (NH
4)
3[RhMo
6O
24H
6] .7H
2O, the assorted polyoxy of a kind of Anderson type is abbreviated as [RhMo in this application for molybdate
6].
Ex3
Repeat Ex1, difference is with aqueous solution of aluminum nitrate (Al (NO
3)
3.9H
2O, Acros Chemicals, 1.16g are dissolved in the 20mL water) replace this first solution, and this second solution is added into 5.01g is dissolved in (NH in the 80mL water
4)
6Mo
7O
244H
2Among the O.This powder is abbreviated as [AlMo
6].
Ex4
Repeat Ex1, difference is the aqueous solution (CuSO with copper sulfate
4.5H
2O, S.D.Fine, 1.50g are dissolved in the 40mL water) replace first solution, and this second solution is added into 10.00g is dissolved in (NH in the 160mL water
4)
6Mo
7O
244H
2O.Reclaim light blue crystalline powder from the 3rd solution, be expressed as [CuMo
6].
Ex5
Repeat Ex1, difference is the aqueous solution (PdCl with Palladous chloride
2, Acros, 0.55g are dissolved in the 20mL water, add 4 concentrated hydrochloric acids (HCl)) and replace first solution, and this second solution is added into 10.00g is dissolved in (NH in the 160mL water
4)
6Mo
7O
244H
2O.Reclaim the yellow crystal powder from the 3rd solution, be expressed as [PdMo
6].
Ex6
By with 2.80g[CoMo
6] (from the Ex1) aqueous solution and 28.05g silica gel (34wt%LUDOX silica gel suspension in deionized water in 25mL water, 158.7 mmole (mmol) silica gel) mix room temperature vigorous stirring 90 minutes, form the solution (combined solution) that merges.The solution of this merging is evaporated to dried at 100 ° of C, obtains dry solid, then 350 ° of C should drying in still air solid calcining 4hr.
Under stirring at room, with wet chemical (K
2CO
3(CDH, 0.29g are dissolved in the 20mL water)) mix with the solid of this sintering of 11.01g, at 100 ° of C the mixture that obtains is evaporated to driedly then, in still air, calcine this dry mixture 4hr at 350 ° of C, obtain catalyzer, be expressed as [CoMo
6]/SiO
2/ K.
(1500 pound per square inch gages (psig) (10.34 MPas (MPa)) tubulose microreactor system evaluation catalyzer is used for synthetic gas (syngas) is changed into the activity of the pure product of mixing to high pressure.This catalyzer of 1.5g is placed the stainless steel reactor that vertically is installed on stove, and (external diameter (O.D.) is the center of 0.25 inch (0.63 centimetre (cm)).Use hot material controller with synthetic gas (carbon monoxide and hydrogen (CO:H
2) ratio be 1:1) be transferred to this reactor from compressed gas cylinder by the activated carbon purification device, by being positioned at the pneumatic back pressure regulator control reactor pressure of reactor downstream.Use electrically heated aluminium block to control temperature of reactor.Before synthetic gas is incorporated into reactor, the hydrogen (H that this catalyzer is being flowed
2) (150 standard cubic centimeter per minute (s-cm
3/ min)) in 330 ° of C pre-treatment 4 hours.After pre-treatment, temperature of reactor is reduced to 270 ° of C, this air-flow is filled to 300s-cm
3The synthetic gas of/min is pressurized to this reactor 1500psig (10.34MPa) then.
Flow through Siemens MAXUM by making Gas-phase reactor flow out stream at environmental stress (normally be 1 normal atmosphere, or 0.1MPa)
TMGas Sampling Valve analysis in the gas-chromatography is from the product of this reactor.For fear of non-volatile product condensation, the pipe downstream things that reactor is all are heated to 160 ° of C.By with PORAPAK
TMThe REOPLEX that the QS post is connected in series
TMPre-column carries out product to be separated.Use the flame ionization detector (FID) of calibration that the outflow stream from the PORAPAK post is carried out quantitatively.The result is summarised in the following table 1.
Ex7
Repeat Ex6, difference is at first with [PdMo
6] aqueous solution (1.41g is dissolved in the 25mL water) and [CoMo of (from Ex5)
6] aqueous solution (1.40g is in 25mL water) of (from Ex1) merges at 90 ° of C, and the solution that will merge is added into 27.99g silica gel.With this K
2CO
3Solution is changed into the K of 0.21g
2CO
3Be dissolved in the 20mL water, and the amount of the powder of the calcining that will mix with it is changed into 12g.This Ex7 makes catalyzer, is expressed as [PdMo
6] [CoMo
6]/SiO
2/ K.
Ex8
Repeat Ex7, difference is with rhodium ammonium molybdate [RhMo
6] aqueous solution (1.41g is dissolved in the 25mL water) of (from Ex2) replaces the palladium ammonium molybdate.The amount of drying solid of calcining is changed into 11g.This Ex8 makes catalyzer, is expressed as [RhMo
6] [CoMo
6]/SiO
2/ K.
Ex9
Repeat Ex8, but use the aluminium ammonium molybdate [AlMo of Ex3
6] the aqueous solution replace the aqueous solution of cobalt ammonium molybdate, with [the RhMo that is dissolved in the 25mL water
6] amount change into 1.40g.This Ex9 makes catalyzer, is expressed as [RhMo
6] [AlMo
6]/SiO
2/ K.
Ex10
Repeat Ex7, but use [AlMo
6] the aqueous solution (1.41g is dissolved in the 25mL water) replace the aqueous solution of palladium ammonium molybdate.This Ex10 makes catalyzer, is expressed as [CoMo
6] [AlMo
6]/SiO
2/ K.
Ex11
Repeat Ex7, but use [CuMo
6] aqueous solution (1.40g is dissolved in the 25mL water) of (from Ex4) replaces [PdMo
6] solution.This Ex11 makes catalyzer, is expressed as [CuMo
6] [CoMo
6]/SiO
2/ K.
Ex12
Repeat Ex11, but use the aqueous solution ((NH of zinc ammonium molybdate
4)
3[ZnMo
6O
24H
6] (1.40g is dissolved in the 25mL water)) replacement [CuMo
6] solution.By repeating Ex4 and using zinc sulfate (ZnSO
4.7H
2O, S.D.Fine 1.73g) replaces copper sulfate (CuSO
4.5H
2O, S.D.Fine 1.50g) synthesizes (NH
4)
3[ZnMo
6O
24H
6], the compound that obtains is expressed as [ZnMo
6].Will with this K
2CO
3The amount of the powder of the calcining that solution mixes is changed into 11g, will be in described solution K
2CO
3Amount change into 0.19g.This Ex12 makes catalyzer, is expressed as [ZnMo
6] [CoMo
6]/SiO
2/ K.
Table 1
MeOH=methyl alcohol; EtOH=ethanol; The PrOH=propyl alcohol; CH
4=methane; C
2=2 carbon atoms; The HC=hydrocarbon; The sel=selectivity; The conv=transformation efficiency; Prod=productivity
Data in the table 1 show that various catalyst compound based on the Anderson heteropoly compound change into synthetic gas the mixture of alcohol effectively, and wherein the result of Ex8 provides especially effectively result.
CEx?A
By stirring under the 10min, with the aqueous solution (Rh (NO of rhodium nitrate with 50rpm
3)
3, (Aldrich, 0.038g are dissolved in the 2mL water)) in dropwise add 1.8g Zirconia-alumina (ZrO to
2-Al
2O
3) carrier, and with 1.8g Zirconia-alumina (ZrO
2-Al
2O
3) carrier floods in room temperature.The carrier of this dipping dry 5 hours of 120 ° of C, is calcined the carrier 4 hours of the dipping of this drying then, thereby obtained catalyzer at 400 ° of C in still air, be expressed as Rh/ZrO
2-Al
2O
3
Use high pressure tubulose microreactor system evaluation catalyzer to be used for the incoming flow of carbon monoxide and hydrogen is changed into the performance of alcohol.This system comprises the stainless steel reaction organ pipe, and the length of this reactor tube is that 14 inches (35.6 centimetres (cm)) and external diameter are 0.25 inch (0.64cm), and it vertically is installed in the electrically heated aluminium block of control temperature of reactor.The catalyzer of 0.25g is placed on the center of reactor tube, and quartz ball is placed on top and the bottom of pipe.With incoming flow gas (CO and H
2) and as the nitrogen (N of interior target from compressed gas cylinder
2) be incorporated into this reactor together, wherein use hot material controller to control incoming flow gas and N
2Flow rate of gas separately.Use the activated carbon purification device to remove any metal carbonyl (metal carbonyls) that may be present in this CO cylinder.Use is arranged in reactor downstream and the pneumatic back pressure regulator control reactor pressure of the line that is connected with reactor.
With incoming flow and N
2Be incorporated into before the reactor, use the H that flows
2(1000mL/hr) preheat this catalyzer 2 hours at 330 ° of C.After this catalyzer of pre-treatment, temperature of reactor is reduced to 280 ° of C, be carbon monoxide (CO) and hydrogen (H with the gas and changing that flows through this reactor
2) (1:1) mixture, and this reactor is pressurized to 1000psig (6.89 MPas (MPa)).Flow through the product that Gas Sampling Valve analysis in the Agilent gas-chromatography (GC) (model 7890A) comes autoreactor by making reactor flow out stream.Pipeline between reactor and the GC is heated to the temperature of 150 ° of C to 180 ° of C, thereby is minimized in the condensation of the lower nonvolatile reaction product of temperature.Flow through three following parallel separate queues and in this GC, carry out product and separate by making reactor flow out stream: a) molecular sieve filled post, and HayeSep
TMThe post that T fills, (b) PoraBOND
TMU capillary column and (c) kapillary CP wax separator column.The automatic control system of using Siemens SIMATIC PCS7 to distribute is used for measuring, control and reactor maintenance system, and the analytical results in the conclusive table 2.
CEx?B
Repeat CEx A, but the amount of rhodium nitrate in the solution is changed into 0.046g, and with magnesium aluminate (MgAl
2O
4) carrier replacement ZrO
2-Al
2O
3Carrier obtains catalyzer, is expressed as Rh/MgAl
2O
4
CEx?C
Repeat CEx A, but the amount of rhodium nitrate in the solution is changed into 0.046g, and add 0.165g Ammonium Heptamolybdate ((NH to this solution
4)
6Mo
7O
24.2H
2O Aldrich), obtains catalyzer, is expressed as RhMo
6/ ZrO
2-Al
2O
3
CEx?D
Repeat CEx C, but the amount of Ammonium Heptamolybdate is reduced to 0.068g and adds 0.098g ammonium metawolframate (ammonium metatungstate, H to this solution
26N
6O
40W
12, Aldrich), obtain catalyzer, be expressed as RhMo
3W
3/ ZrO
2-Al
2O
3
Ex13
Repeat CEx A, but this carrier is changed into 0.9g gama-alumina (Aldrich), this aqueous solution is changed into 0.1g from the [RhMo of Ex2
6] solution of catalyzer in 2mL water, to calcine pressure and catalyzer and carry out calcining pressure and the catalyzer execution pressure that pressure (catalyst performance pressure) is changed into Ex1, and pretreatment time changed into 3 hours, thereby obtain by [RhMo
6]/Al
2O
3The catalyzer of expression.
Use the parallel fixed-bed reactor of high pressure (PFBR) (PFBR System P/N; 132088, from Symyx
TMTechnologies Inc), the module reactor that is constituted by three compartments (it contains 16 reactor tubes separately) evaluate catalysts performance.Pipe in each compartment is enclosed in the stainless steel mitriform cup, and this mitriform cup can enough nitrogen (N
2) used uniform pressure supercharging in reacting with each.In reactor tube, load 200 microlitres (μ L) catalyzer, use 90 volume % (vol%) per-cent (vol%) hydrogen (H
2) and 10vol%N
2Gaseous mixture, with this catalyzer at 1500psig 330 ° of C (heating rate is 5 ° of C per minutes) in-situ reducing 3 hours, each vol% is based on total gaseous mixture volume.Catalyzer is cooled to 280 ° of C.
At the pressure of 1500psig, the temperature shown in the table 3 and 6250h
-1GHSV, use carbon monoxide (CO) and hydrogen (H
2) incoming mixture (1:1v/v%) test this catalyzer.At 320 ° of C but continue test at the pressure of 90 bar (9MPa), then pressure is back to 35 bar (3.5MPa) and tests at 340 ° of C.Use Siemens technology GC evaluation response organ pipe to flow out stream.Repeat the circulation of twice this catalyst test more in addition and the mean value of three test loop is given test result in table 3.
Ex14
Repeat Ex13, but carrier is changed into the SiO of 0.9g
2(Aldrich) thus obtain by [RhMo
6]/SiO
2The catalyzer of expression.
Ex15
Repeat Ex13, but carrier is changed into the TiO of 0.9g
2(Aldrich) thus the catalyzer that obtains being expressed from the next: [RhMo
6]/TiO
2
Ex16
Repeat Ex13, but carrier is changed into the ZrO of 0.9g
2(Aldrich)) thus the catalyzer that obtains being expressed from the next: [RhMo
6]/ZrO
2
Ex17
By with 5mL/ minute the speed aqueous solution (K with salt of wormwood
2CO
3(0.277mol is dissolved in the 250mL water for CDH, 44.08g)) be added into 70 ° of C zirconium nitrate (ZrO (NO of stirring
3)
22H
2O (Aldrich, 1.50g, 6.49mmol)) and aluminum nitrate (contain the Al (NO that is dissolved in the 1000mL water
3)
39H
2In the two the aqueous solution of O (S.D.Fine, 51.75g, 0.09mol)) and the Zirconia-alumina throw out that preparation mixes.After three hours, by filtering and with hot water (90 ° of C) repeated washing four times, reclaiming this throw out.The throw out that makes this washing was calcined this dry throw out 4 hours at 450 ° of C then, thereby is obtained being called ZrO dry 5 hours of 120 ° of C in still air
2-Al
2O
3Compound.The K that adds as precipitation agent is removed in washing effectively from throw out
2CO
3
Repeat Ex13, but this matrix is changed into ZrO
2-Al
2O
3Compound, thus compound obtained, be expressed as [RhMo
6]/ZrO
2-Al
2O
3The results are summarized in the table 2 of 1000psig (6.89MPa), at the table 3 that the results are summarized in of 1500psig (10.34MPa), in 4 and 5.
Ex18
By with magnesium nitrate (Mg (NO
3)
26H
2O (4mmol is dissolved in the 20mL water for S.D Fine, 1.03g)) and aluminum nitrate (Al (NO
3)
39H
2O (8mmol is dissolved in the 30mL water for Aldrich, 3.00g)) the aqueous solution is added in the aqueous solution (0.08mol is dissolved in the 20mL water for S.D.Fine, 4.80g) that contains urea and prepares the solution of this merging.The solution of this merging is transferred in the 100mL teflon-coating autoclave, seal this autoclave and and with its content 180 ° of C heating 20 hours.The content of this autoclave is cooled to envrionment temperature, by the filtered and recycled throw out, washes this throw out three times with water.At 100 ° of C dry throw out 1 hour that should washing in air furnace, in still air, calcined this dry throw out 4 hours at 700 ° of C then, obtain compound, be called magnesium aluminate or MgAl
2O
4
Repeat Ex13, but matrix is changed into MgAl
2O
4Thereby, obtain compound, be expressed as [RhMo
6]/ZrO
2-Al
2O
3The results are summarized in table 3,5 and 6.
Ex19
With molybdenum oxide (MoO
3, SD Fine, 0.49g, 3.41mmol) and sodium wolframate (Na
2WO
4.2H
2O, Chemport, 1.12g, 3.41mmol) combined heated in 80mL water is to boiling.With rhodium nitrate (Aldrich, 0.32g 1.03mmol) aqueous solution that is dissolved in the 20mL water dropwise is added in the above solution, thereby forms the mixture that merges, make the mixture of this merging 80 ° of C standing over night then, thereby allow that solid crystallizes out from solution.With this solid recrystallization twice from water, thereby obtain compound, be expressed as [RhW
3Mo
3].
In room temperature, the MgAl that 0.9g is identical with Ex18
2O
4Matrix [RhW
3Mo
3] the aqueous solution (0.1g is dissolved in the 2mL water) dipping, the matrix of dry and this dipping of calcining as among the Ex17 is preserved for calcining temperature is reduced to 350 ° of C then, obtains compound, is expressed as [RhW
3Mo
3]/MgAl
2O
4According to CEx A evaluate catalysts performance, and in table 2, provide.According to Ex13 evaluate catalysts performance, and will the results are summarized in the table 5.
Ex20
Use the device of CEx A, one of them modification is to allow that incoming flow contains ethene, and another process of revising CEx A changes the evaluating catalyst catalyst performance that uses Ex19 into.Modification on the process is: a) amount with catalyzer increases to 0.35g; B) ethene is changed in incoming flow, CO, H
2And N
2Mixture, volume ratio separately is 5:45:45:5; C) with pressure change for reactor is pressurized to 35 bar (3.5 MPas (MPa)) or 90 bar (9.0MPa), as shown in table 7 below; And d) uses the temperature shown in the table 7.The results are summarized in the table 7.
Ex21
Repeat Ex19, still matrix is changed into the zirconium white-aluminate (zirconia-aluminate) as the mixing for preparing among the above Ex17, thereby obtained compound, be expressed as [RhW
3Mo
3]/ZrO
2-Al
2O
3According to Ex13 evaluate catalysts performance, will the results are summarized in the table 5.
Ex22
To contain the cesium carbonate that is dissolved in 200 μ L water (Aldrich, 0.09mmol), yellow soda ash (Aldrich, 0.09mmol) and the aqueous solution of Quilonum Retard (Aldrich, 0.09mmol)) be added into 200 milligrams (mg) as [RhMo prepared among the Ex18
6]/MgAl
2O
4In, thereby the compound of formation modification.In still air, calcine the compound four hours of this modification at 350 ° of C, thereby obtain compound, be expressed as [RhMo
6]-Cs-Na-Li/MgAl
2O
4Also will the results are summarized in the table 2 in 1000psig (6.89MPa) evaluate catalysts performance according to Ex17, also will the results are summarized in the table 6 in 1500psig (10.34MPa) evaluate catalysts performance according to Ex17.
Ex23
Repeat Ex22, but the aqueous solution is changed into salt of wormwood (Aldrich, 0.03mmol are dissolved in the water of 200 μ L), obtain compound, be expressed as [RhMo
6]-K/MgAl
2O
4, only estimate at 1500psig (10.34MPa), and will the results are summarized in the table 6.
Ex24
Repeat Ex23, (Aldrich 0.09mmol) is dissolved in solution in the 200 μ L water, obtains compound, is expressed as [RhMo but the aqueous solution is changed into Quilonum Retard
6]-Li/MgAl
2O
4, and will the results are summarized in the table 6.
Ex25
In room temperature, with the aqueous solution (CoSO of rose vitriol
4.4H
2O (3.7mmol is dissolved in the 8mL water for S.D.Fine, 1.04g)) adds 30%H to
2O
2(Ran Kem 0.5g) forms first solution.Under agitation, with the aqueous solution ((NH of ammonium molybdate
4)
6Mo
7O
24.4H
2O) (6.2mmol is in 65mL water for SD Fine, 7.65g) is added into this first solution.As above among the Ex19, recovering crystals matter [CoMo
6].
In room temperature, with 0.9g ZrO
2-Al
2O
3With [the RhMo that contains 0.05g Ex2
6] and [CoMo for preparing in the present embodiment of 0.05g
6] aqueous solution dipping of (the two all is dissolved in the 1mL water).As among the Ex19, the material of drying and this dipping of calcining obtains compound, is expressed as [RhMo
6] [CoMo
6]/ZrO
2-Al
2O
3At 1500psig (10.34MPa) and 7000 hours inverse (h
-1) gas hourly space velocity (GHSV) evaluate catalysts performance, and analytical results is summarized in the following table 4.
Ex26
Repeat Ex25, difference is with chrome molybdenum [CrMo
6] preparation of crystalline material replaces [CoMo
6] preparation of material.First solution is the aqueous solution (Cr of chromium sulphate
2(SO
4)
3.4H
2O (3.1mmol is dissolved in the 20mL water for CDH, 1.44g)).Under agitation, this first solution is added into (NH
4)
6Mo
7O
24.4H
2The aqueous solution of O (SD Fine, 5.20g, 4.2mmol,, in 80mL water).As among the above Ex19, recovering crystals matter [CrMo
6].Repeat to be expressed as [RhMo
6] [CrMo
6]/ZrO
2-Al
2O
3Compound.Analytical results is summarized in the following table 4.
Ex27
Repeat Ex25, difference is with iridium molybdenum [IrMo
6] preparation of material replaces [CoMo
6] preparation of material.The aqueous solution (the IrCl that this first solution is iridium chloride
3, S.D.Fine, 0.6306g, 1.888mmol is dissolved in the 10mL water).Under agitation, this first solution is added into (NH
4)
6Mo
7O
24.4H
2In the aqueous solution of O (1.62mmol is in 40mL water for SD Fine, 2g).Use the process of describing in detail among the above Ex19, recovering crystals matter is called [IrMo
6].Repeat to be expressed as [RhMo
6] [IrMo
6]/ZrO
2-Al
2O
3Compound.Analytical results is summarized in following table 4.
Ex28
Repeat Ex25, difference is with nickel molybdenum [NiMo
6] preparation of material replaces [CoMo
6] preparation of material.The aqueous solution (the NiSO that this first solution is single nickel salt
4.4H
2O (7.40mmol is dissolved in the 20mL water for S.D.Fine, 1.14g)).Under agitation, this first solution is added into (NH
4)
6Mo
7O
24.4H
2The aqueous solution of O (6.34mmol is in 100mL water for SD Fine, 7.83g).Use the process of describing in detail among the above Ex19, recovering crystals matter is called [NiMo
6].Repeat to be expressed as [RhMo
6] [NiMo
6]/ZrO
2-Al
2O
3Compound.Analytical results is summarized in the following table 4.
Ex29
Repeat Ex25, difference is with palladium molybdenum [PdMo
6] preparation of material replaces [CoMo
6] preparation of material.The aqueous solution (the PdCl that this first solution is Palladous chloride
2(3.1mmol is dissolved in the 20mL water for Aldrich, 0.5497g)).Under agitation, this first solution is added into (NH
4)
6Mo
7O
24.4H
2The aqueous solution of O (4.2mmol is in 80mL water for SD Fine, 5.19g).Use the process of describing in detail among the above Ex19, recovering crystals matter is called [PdMo
6].Repeat to be expressed as [RhMo
6] [PdMo
6]/ZrO
2-Al
2O
3Compound.Analytical results is summarized in the following table 4.
Ex30
Under agitation, with the aqueous solution (ReCl of chlorination rhenium
3(Aldrich, 0.08g are dissolved in the 6mL water)) and 1g ZrO
2-Al
2O
3Merge.Use Rotary Evaporators evaporating solvent from the material of this merging to stay solid residue.Drying and calcining obtain being expressed as Re/ZrO described in Ex17
2-Al
2O
3Carrier.
With [the RhMo of 0.05g from Ex2
6] the aqueous solution in 6mL water dropwise is added into this carrier, dry and this carrier of calcining as among the Ex19 is expressed as [RhMo then
6] Re/ZrO
2-Al
2O
3Compound.Analytical results is summarized in the following table 4.
Ex31
At room temperature (25 ° of C), with the aqueous solution (RhCl of rhodium chloride
3(0.78mmol is dissolved in the 10mL water for Aldrich, 0.20g)) and the aqueous solution ((NH of ammonium metawolframate (ammonium meta-tungstate)
4)
6W
12O
41.xH
2O, SD Fine, 1.1457g, 0.3876mmol is in 50mL water) stir together.Use the process of describing in detail among the above Ex19, recovering crystals matter is called [RhW
6].
In room temperature, with [RhW
6] the aqueous solution (0.1g is dissolved in the 2mL water) dipping 0.9g and Ex18 in identical MgAl
2O
4Base material, the matrix that makes this dipping calcine matrix this drying, that flood 4 hours at 350 ° of C then dry 5 hours of 120 ° of C in still air, be expressed as [RhW
6]/MgAl
2O
4Compound.In 1500psig (10.34MPa) evaluate catalysts performance, will the results are summarized in the following table 5 as mentioned above.
Ex32
Repeat Ex20, difference is to use the catalyzer from Ex31.To the results are summarized in the following table 7.
Ex33
Repeat Ex31, difference is that matrix is changed into zirconium white-aluminate (zirconia-aluminate) as mixing prepared among the above Ex17, thereby is expressed as [RhW
6]/ZrO
2-Al
2O
3Compound.Evaluating catalyst be the results are summarized in the following table 5.
Ex34
Repeat Ex25, difference is to use MgAl
2O
4Replace ZrO
2-Al
2O
3With with iron molybdenum [FeMo
6] preparation of crystalline material replaces [CoMo
6] preparation of material.The aqueous solution (the NH that this first solution is ferric ammonium sulfate
4Fe (SO
4)
2.12H
2O (3.1mmol is dissolved in the 20mL water for Aldrich, 1.5g)).Under agitation, this first solution is added into (NH
4)
6Mo
7O
24.4H
2The aqueous solution of O (4.2mmol is in 80mL water for SD Fine, 5.20g).Use the process of describing in detail among the above Ex19 to reclaim and be called [FeMo
6] crystalline material.Repeat to be expressed as [RhMo
6] [FeMo
6]/MgAl
2O
4Compound.Analytical results is summarized in the following table 4.
Ex35
Repeat Ex20, difference is to use the catalyzer that comes from Ex34.To the results are summarized in the following table 7.
Table 2
S (Alc)=to the selectivity of whole alcohol, S (HC)=to the selectivity of whole hydrocarbon, S (p-ROH)=to the selectivity of primary alconol (ethanol+propyl alcohol).Each selective meter is shown and does not contain CO
2Value.
Data in the table 2 will be based on [RhMo
6] catalyzer of Anderson heteropoly compound compares with the performance that contains the catalyzer of Rh and Rh-Mo, wherein Rh or Rh and Mo content equal [RhMo
6] those content of catalyzer.By means of ZrO
2-Al
2O
3Carrier, Ex17 based on [RhMo
6] catalyzer bigger CO transformation efficiency and bigger to whole alcohol (totally) and primary alconol (specifically) selection of them, than the Rh catalyzer of CEx A or the RhMo catalyzer of CEx C is provided.By means of MgAl
2O
4Carrier, Ex19 based on [RhW
3Mo
3] catalyzer aspect the parameter of measuring, demonstrate much better result than the Rh catalyzer of CEx B, and at the RhMo that aspect the selectivity of primary alconol, demonstrates than CEx D
3W
3The result that catalyzer is good.
Table 3
S (Alc)=to the selectivity of whole alcohol, S (HC)=to the selectivity of whole hydrocarbon, S (p-ROH)=to the selectivity of primary alconol (ethanol+propyl alcohol).Every kind of selective meter is shown and does not contain CO
2Value.
Data in the table 3 show the carrier MgAl for example that uses modification
2O
4And ZrO
2-Al
2O
3(Ex17 and 18) is than using conventional carrier such as Al
2O
3(Ex13), SiO
2(Ex14), ZrO
2(Ex16) and TiO
2(Ex15), far better aspect the selectivity of primary alconol.
Table 4. uses the experiment of the Anderson that mixes
S (Alc)=to the selectivity of whole alcohol, S (HC)=to the selectivity of whole hydrocarbon, S (p-ROH)=to the selectivity of primary alconol (ethanol+propyl alcohol).Every kind of selective meter is shown and does not contain CO
2Value.
Data in the table 4 show for example [CrMo of available non-Rh Anderson type precursor
6] (Ex26), [NiMo
6] (Ex28), [CoMo
6] (Ex25), [PdMo
6] (Ex29) or [IrMo
6] (Ex27) described [RhMo of instead of part
6], perhaps for example the Re modification should [RhMo with metal
6] (Ex30), all pass through to eliminate this more and more expensive and more and more unobtainable metal of a certain amount of Rh in each case, and reduce the cost of catalyzer, but also have the loss of some catalyst performances simultaneously.Ex34 shows and is supported on and Al
2O
3The Anderson mixture of the mixing on the different materials also provides satisfied result.
The Anderson precursor that table 5.Mo-W mixes
S (Alc)=to the selectivity of whole alcohol, S (HC)=to the selectivity of whole hydrocarbon, S (p-ROH)=to the selectivity of primary alconol (ethanol+propyl alcohol).Every kind of selective meter is shown and does not contain CO
2Value.
Data in the table 5 show, though all embodiment provide satisfied result, than other combination shown in the table 5, based on catalyst composition and the MgAl of the metal A nderson type heteropoly compound that mixes
2O
4The combination of carrier (Ex19) provides unexpected more excellent result.
Table 6. adds the effect of alkali
S (Alc)=to the selectivity of whole alcohol, S (HC)=to the selectivity of whole hydrocarbon, S (p-ROH)=to the selectivity of primary alconol (ethanol+propyl alcohol).Every kind of selective meter is shown and does not contain CO
2Value.
Data in the table 6 show, for the same catalyst that does not have alkali metals modified (Ex18), alkali metals modified (Ex22-24) causes increasing to the selectivity of alcohol or increases selectivity to primary alconol.Even without alkali metals modified, the data of Ex18 also are gratifying.
The effect of the common charging of ethene that table 7. is other
S refers to selectivity
Data in the table 7 show for for the charging that also contains ethene carbon monoxide and the hydrogen, are effective based on the catalyzer of Anderson type heteropoly compound.
Claims (8)
1. be used for synthetic gas is changed into the method for oxide compound, described method comprises that the mixture that makes hydrogen and carbon monoxide and the Anderson type Heterocompound catalyst that contains transition metal contact under the condition of the temperature, pressure and the gas hourly space velocity that are enough to described mixture is changed at least a alcohol, wherein said alcohol contains 1 to 6 carbon, and described catalyzer has general formula (A)
x[M
1Mo
yW
6-y] M
2The structure of expression, wherein A is H
+, ammonium ion, or alkalimetal ion, M
1Be following at least a: aluminium, the transition metal of zinc or chosen from Fe, ruthenium, chromium, rhodium, copper, cobalt, nickel, palladium and iridium, M
2Be the properties-correcting agent of choosing wantonly, it is to be selected from following at least a metal: basic metal, alkaline-earth metal and be selected from the transition metal of rhenium, chromium, palladium, nickel, iridium and cobalt, x are that 3 to 4 integer and y are 0 to 6 integers.
2. the process of claim 1 wherein that described catalyzer comprises the mixture of at least two kinds of Anderson type Heterocompound catalysts, M in first kind
1Be rhodium, M in second kind
1Be selected from cobalt, iridium, copper, nickel, palladium, zinc, aluminium, iron, chromium and ruthenium.
3. claim 1 or 2 method, wherein said catalyzer also comprises the carrier of at least a support of the catalyst and modification, described support of the catalyst is selected from silicon-dioxide, aluminum oxide, titanium oxide, Tungsten oxide 99.999, zirconium white, magnesium oxide, zinc oxide or its mixture, the carrier of described modification is selected from silicon-dioxide and the aluminum oxide of zirconium white modification, magnesium aluminate, Zinc aluminate and magnesium-modified silicon-dioxide and aluminum oxide.
4. each method in the claim 1 to 3, the condition of wherein said temperature, pressure and gas hourly space velocity comprises following at least a: temperature is 200 ° of C to 450 ° of C, pressure be 200psig (1.38MPa) to 4,000psig (24.58MPa), or gas hourly space velocity is 300hr
-1To 25,000hr
-1
5. each method in the claim 1 to 4, wherein the hydrogen that has of the mixture of hydrogen and carbon monoxide and the ratio of carbon monoxide are 10:1 to 1:10.
6. each method, wherein M in the claim 1 to 5
1Be the combination of cobalt and palladium, the combination of cobalt and rhodium, the combination of aluminium and rhodium, the combination of cobalt and aluminium, the combination of copper and cobalt, and the combination of zinc and cobalt and y are 6.
7. each method in the claim 1 to 6, wherein the mixture of carbon monoxide and hydrogen also comprises alkene.
8. the method for claim 7, wherein said alkene is ethene.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US39173510P | 2010-10-11 | 2010-10-11 | |
| US61/391,735 | 2010-10-11 | ||
| PCT/US2011/053197 WO2012050804A1 (en) | 2010-10-11 | 2011-09-26 | The use of anderson -type heteropoly compound - based catalyst compositions in the conversion of synthesis gas to oxygenates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103249702A true CN103249702A (en) | 2013-08-14 |
| CN103249702B CN103249702B (en) | 2015-05-06 |
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ID=44801162
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|---|---|---|---|
| CN201180059003.7A Expired - Fee Related CN103249702B (en) | 2010-10-11 | 2011-09-26 | The use of Anderson -type heteropoly compound - based catalyst compositions in the conversion of synthesis gas to oxygenates |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US8598239B2 (en) |
| EP (1) | EP2627621B1 (en) |
| CN (1) | CN103249702B (en) |
| BR (1) | BR112013006995A2 (en) |
| WO (1) | WO2012050804A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106252652A (en) * | 2015-06-05 | 2016-12-21 | 惠州市豪鹏科技有限公司 | The preparation method of a kind of positive electrode active materials, positive plate and lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6037305B2 (en) * | 2012-12-27 | 2016-12-07 | 積水化学工業株式会社 | C2 oxygenate synthesis catalyst, C2 oxygenate production apparatus, and C2 oxygenate production method |
| WO2017204975A1 (en) * | 2016-05-26 | 2017-11-30 | Exxonmobil Chemical Patents Inc. | Oxygenate synthesis and homologation |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4749724A (en) * | 1983-03-18 | 1988-06-07 | The Dow Chemical Company | Process for producing alcohols from synthesis gas |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4210597A (en) | 1979-05-14 | 1980-07-01 | Ethyl Corporation | Preparation of oxygenates from carbon monoxide and hydrogen |
| GB8334155D0 (en) | 1983-12-22 | 1984-02-01 | Ici Plc | Catalytic composition |
| US4825013A (en) | 1984-11-05 | 1989-04-25 | The Dow Chemical Company | Preparation of ethanol and higher alcohols from lower carbon number alcohols |
| US4607056A (en) | 1985-07-03 | 1986-08-19 | Texaco Inc. | Mixed aliphatic alcohol production |
| US4616040A (en) | 1985-07-22 | 1986-10-07 | Texaco Inc. | Production of C2 -C6 aliphatic alcohols |
| US7923405B2 (en) * | 2007-09-07 | 2011-04-12 | Range Fuels, Inc. | Cobalt-molybdenum sulfide catalyst materials and methods for ethanol production from syngas |
-
2011
- 2011-09-26 BR BR112013006995-3A patent/BR112013006995A2/en not_active IP Right Cessation
- 2011-09-26 CN CN201180059003.7A patent/CN103249702B/en not_active Expired - Fee Related
- 2011-09-26 US US13/825,607 patent/US8598239B2/en not_active Expired - Fee Related
- 2011-09-26 EP EP11770242.3A patent/EP2627621B1/en not_active Not-in-force
- 2011-09-26 WO PCT/US2011/053197 patent/WO2012050804A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4749724A (en) * | 1983-03-18 | 1988-06-07 | The Dow Chemical Company | Process for producing alcohols from synthesis gas |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106252652A (en) * | 2015-06-05 | 2016-12-21 | 惠州市豪鹏科技有限公司 | The preparation method of a kind of positive electrode active materials, positive plate and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| BR112013006995A2 (en) | 2020-11-24 |
| WO2012050804A1 (en) | 2012-04-19 |
| EP2627621B1 (en) | 2016-08-17 |
| US20130190411A1 (en) | 2013-07-25 |
| EP2627621A1 (en) | 2013-08-21 |
| CN103249702B (en) | 2015-05-06 |
| US8598239B2 (en) | 2013-12-03 |
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